Hair treatment gels containing itaconic acid monoester/acrylate copolymer

ABSTRACT

The aqueous hair treatment gel contains a combination of at least one itaconic acid monoester/acrylate copolymer and at least one non-ionic, anionic, zwitterionic or amphoteric hair-fixing polymer. The itaconic acid monoester has a formula CH 2 ═C(COOR 1 )CH 2 COOR 2 , wherein one of R 1  and R 2  represents hydrogen and the other represents —(CH 2 CH 2 O) x —R 3 , x is a number between 1 to 100 and R 3  is an alkyl group having 8 to 30 carbon atoms. The aqueous hair treatment gel has a pH of greater than 7 and a viscosity of greater than 500 mPa.s, as measured at 25° C.

BACKGROUND OF THE INVENTION

[0001] The subject matter of the invention is a hair treatmentcomposition in gel form containing an itaconic acid monoester/acrylatecopolymer and a hair-fixing film-forming polymer, which haspredetermined rheologic properties.

[0002] Hair gels are used for holding and fixing human hair.Conventional hair gels usually contain a combination of gel formers andhair-fixing polymers. The cosmetic hair-fixing polymers usually used forthis purpose are characterized by good fixing properties, which more orless satisfactorily hold and fix the hair in a predetermined shape, inaqueous, alcoholic or aqueous-alcoholic media. Frequently however thehair is provided with an only unsatisfactory luster by application ofthese hair-fixing polymers. Of course a series of additives are known,which are in a position to improve the hair luster, e.g. hydrophobicmaterials, such as liquid paraffins, isoparaffins, silicone oils orhydrophilic materials, such as multivalent alcohols, especially glycerolor polypropylene glycol. The known luster giving materials frequentlydisadvantageously affect other desired properties of the hair gel. Theycan act as a softener for the fixing polymer used and thus reduces itsfixing power. They can impair the clarity and transparency of the gel,the rheological properties and correspondingly the applicationproperties. Alternatively they still do not provide sufficient hairluster.

[0003] An additional important property of hair gel is its rheologicalbehavior. Gels, on the one hand, have high viscosity, and, on the otherhand, have the properties of non-Newtonian liquids, especially theproperties of pseudo-plastic liquids with or without a flow limit. Theviscosity deceases with increasing shear rate (shear thinning) and theflow curve is non-linear, i.e. the ratio of the shear stress or shearingforce to the shear rate is not constant. This is observable in practicebecause a gel with these properties has a comparatively high viscosityin the resting phase and/or plastic behavior, but flows readily onapplication of a comparatively small force and thus is easily removedfrom its packaged and easily distributed over the hair. Typically andfrequently used gel formers, which form gels having a viscosity thatdecreases under pressure, are neutralized carbomers (polyacrylic acid).

[0004] The viscosity decrease of conventional hair gels caused by shearstress due to their own weight is a disadvantage of these conventionalhair gels. Because of that decrease the hair gels can flow. Then thecomposition can drip from an opened tube containing it even without anexternally applied pressure. Also it can run off vertical or inclinedskin or hair surfaces after manual application and, in the case of a gelwith thixotropic behavior, even with an increased speed. Undesireddripping or run off of course can be naturally avoided by increasing thebase viscosity. However at the same time the application properties,e.g. the distributability and workability of the composition into thehair, are impaired and greater amounts of gel formers are required,which can lead to increased product costs and to increased load on thehair.

SUMMARY OF THE INVENTION

[0005] It is an object of the present invention to provide a hairtreatment gel of the above-described type, which avoids thedisadvantages of the prior art hair treatment gels.

[0006] It is a further object of the present invention to provide a hairtreatment gel, which provides good hair fixing but at the same timeoptimizes hair luster, avoids the rheological disadvantages ofconventional hair gels and has more attractive, more pleasing hapticproperties.

[0007] It has now been found that these objects can be attained with ahair treatment gel on an aqueous basis, which has a viscosity of atleast 1000 mPa.s at 25° C., a pH of greater than 7 and which containsthe following combination of ingredients:

[0008] (A) at least 0.5 percent by weight of at least one copolymer of afirst monomer and a second monomer, wherein the first monomer is anitaconic acid monoester of the formula CH₂═C(COOR¹)CH₂COOR², wherein oneof R¹ and R² represents hydrogen and the other of R¹ and R² representsthe group —(CH₂CH₂O)_(x)—R³, x is a number between 1 to 100 and R³ is analkyl group with 8 to 30 carbon atoms, and the second monomer is anacrylate monomer; and

[0009] (B) at least one non-ionic, anionic, zwitterionic or amphoterichair-fixing polymer;

[0010] but which does not contain a combination of anacrylate/Ceteth-20-itaconate copolymer, cellulose acetate phthalate andHO—(CH₂CH₂O)₇₅—(CH(CH₃)CH₂O)₃₀—(CH₂CH₂O)₇₅—H.

[0011] The copolymer (A) is preferably present in an amount of from 0.5to 20, preferably from 1.5 to 10, percent by weight and the hair-fixingpolymer (B) is present preferably in an amount of 0.1 to 15, preferablyfrom 0.5 to 10, percent by weight. The hair gel according to theinvention is preferably essentially free of cationic polymers, i.e. itcontains either no cationic polymers or less than 0.02 percent by weightof cationic polymers. The hair gel according to the invention providesgood hair fixing and an improved hair luster at the same time asimproved flow properties and an especially pleasant appearance.

[0012] It has now been found that these objects may also be attainedwith a hair treatment gel on an aqueous basis, which has a viscosity ofat least 1000 mPa.s at 25° C., a pH of greater than 7 and which containsthe following combination of ingredients:

[0013] (a) an acrylate/Ceteth-20-itaconate copolymer,

[0014] (b) cellulose acetate phthalate, and

[0015] (c) HO—(CH₂CH₂O)₇₅—(CH(CH₃)CH₂O)₃₀—(CH₂CH₂O)₇₅—H.

[0016] The term “alkyl” in the present disclosure means “monovalenthydrocarbon groups”, which can be linear, branched or cyclic.

Copolymer (A)

[0017] The copolymer (A) is built up from itaconic acid monoesters ofthe general formula CH₂═C(COOR¹)CH₂COOR², wherein one of R¹ and R²represents hydrogen and the other of R¹ and R² represents the group—(CH₂CH₂O)_(x)—R³, x is a number between 1 to 100, preferably from 10 to40, especially preferably 20. R³ is an alkyl group with 8 to 30,preferably 12 to 20, carbon atoms, especially cetyl or stearyl arepreferred.

[0018] The acrylate monomers of the copolymer (A) are preferablyselected from the group consisting of acrylic acid, methacrylic acid andtheir esters, especially the acrylic acid alkyl esters and methacrylicacid alkyl esters with one to ten, especially 1 to 4, carbon atoms inthe alkyl group. Suitable copolymers are, for example, acrylic acid ormethacrylic acid/itaconic acid polyethoxyalkyl ester copolymers (INCIname:acrylates/Steareth-20 itaconate coplymer and acrylates/Ceteth-20itaconate copolymer), such as marketed by the firm National Starch,U.S.A. under the trademark Structure® 2001 and Structure® 3001. The acidgroups in the polymers used are preferably neutralized by organic orinorganic bases to the extent of 50 to 100%. Suitable neutralizationagents are primary or secondary amines, especially aminoalkanols withpreferably from 1 to 10 carbon atoms and 1 to 3 hydroxy groups, such ase.g. aminomethyl propanol (AMP), triethanol amine,tetrahydroxypropylethylenediamine or monoethanolamine, but also ammonia,sodium hydroxide, potassium hydroxide, among others.

Hair-Fixing Polymer (B)

[0019] The hair-fixing polymer (B) can be non-ionic, anionic,zwitterionic or amphoteric, however preferably anionic or nonionic. Itcan be a synthetic or natural polymer. The term “natural polymer” meansany polymer of natural origin or any polymer of natural origin that hasbeen chemically modified. Those polymers are particularly preferred,which have sufficient solubility in water, alcohol or alcohol/watermixtures, in order to be present in completely dissolved form in thecompositions according to the invention. “Hair-fixing polymers” areunderstood to be those polymers, which, when used in an amount of from0.01 to 5% in an aqueous, alcoholic or aqueous-alcoholic solution ordispersion, are in a position to deposit a polymer film on the hair andto fix the hair.

[0020] Suitable synthetic non-ionic polymers include homopolymers orcopolymers, which are built up from at least one of the followingmonomers:

[0021] vinylpyrrolidone, vinylcaprolactam, vinyl esters, such as vinylacetate, vinyl alcohol, acrylamide, methacrylamide, alkyl- anddialkylacrylamide, alkyl- and dialkylmethacrylamide,dialkylaminoalkylmethacrylamide, dialkylaminoalkylacrylamide,alkylacrylate, alkylmethacrylate, propylene glycol or ethylene glycol,wherein the alkyl groups in these monomers preferably have from one toseven carbon atoms, especially preferably from one to three carbonatoms. For example, homopolymers of vinyl caprolactam, of vinylpyrrolidone or of N-vinylformamide, are especially suitable. Additionalsuitable synthetic non-ionic film-forming hair-fixing polymers are,e.g., copolymerizates of vinyl pyrrolidone and vinyl acetate,terpolymers of vinyl pyrrolidone, vinyl acetate and vinyl propionate,terpolymers of vinyl pyrrolidone, vinyl caprolactam anddialkylaminoalkyl(meth)acrylate, terpolymers of vinyl pyrrolidone, vinylcaprolactam and dialkylaminoalkyl(meth)acrylamide, polyacrylamide,polyvinyl alcohols, and hair-fixing polyethylene glycol/polypropyleneglycol copolymers. Polyvinylpyrrolidone and polyvinylpyrrolidone/vinylacetate copolymers are especially preferred.

[0022] Suitable anionic hair-fixing polymers include natural orsynthetic homo- or copolymers with monomer units containing acid groups,which are copolymerizable with comonomers, if necessary, which containno acid groups. The acid groups preferably include —COOH, —SO₃H, —OSO₃H,—OPO₂H and —OPO₃H groups, of which the carboxylic acid groups areespecially preferred. The acid groups of these anionic polymers can bepresent in partially or completely neutralized form. They are present inthe composition according to the invention in a form that is 50%neutralized or in a completely neutralized form. The above-mentionedneutralizing agents may be used to neutralize the acid groups. Suitablemonomers include unsaturated, radically polymerizable compounds, whichhave at least one acid group, especially carboxyvinyl monomers. Suitablemonomers containing acid groups include, e.g., acrylic acid, methacrylicacid, crotonic acid, maleic acid and/or maleic acid anhydride or theirmonoesters, aldehydocarboxylic acids or ketocarboxylic acids.

[0023] Comonomers not substituted with acid groups include, e.g., acrylamide, methacrylamides, alkyl and dialkylacrylamides, alkyl anddialkylmethacrylamides, alkylacrylates, alkylmethacrylates, vinylcaprolactone, vinyl pyrrolidone, vinyl esters, vinyl alcohol, propyleneglycol or ethylene glycol, amine-substituted vinyl monomers, such asdialkylaminoalkylacrylates, dialkylaminoalkylmethacrylates,monoalkylaminoalkylacrylates and monoalkylaminoalkylmethacrylates, inwhich the alkyl groups of these monomers preferably contain one to sevencarbon atoms, especially preferably from one to three carbon atoms.

[0024] Suitable anionic polymers especially include copolymers ofacrylic acid or methacrylic acid with monomers selected from the groupconsisting of acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides and vinylpyrrolidones, homopolymers of crotonicacid and copolymers of crotonic acid with monomers selected from thegroup consisting of vinyl esters, acrylic acid esters, methacrylic acidesters, acrylamides and methacrylamides. A suitable natural polymer is,for example, shellac.

[0025] Preferred anionic polymers include cross-linked or uncross-linkedvinyl acetate/crotonic acid copolymers. Similarly partially esterifiedcopolymers between vinyl methyl ether and maleic acid anhydride are alsopreferred. Additional suitable anionic polymers include, e.g.,terpolymers of acrylic acid, alkyl acrylate and N-alkylacrylamide,especially acrylic acid/ethyl acrylate/N-t-butylacrylamide terpolymer,terpolymers of vinyl acetate, crotonate and vinyl alkanoate, especiallyvinyl acetate/crotonate/vinyl neodecanoate copolymers.

[0026] Suitable film-forming amphoteric polymers include those polymers,which contain both basic or cationic groups, especially primary,secondary and tertiary amine groups, besides acidic or anionic groups,as additional functional groups. For example, suitable amphotericpolymers are copolymers made from alkylacrylamides (especiallyoctylacrylamide), alkylaminoalkylmethacrylates (especiallyt-butylamino-ethylmethacrylate), and two or more monomers selected fromthe group consisting of acrylic acid, methacrylic acid and their esters,in which the alkyl groups have from one to four carbon atoms and atleast one of the monomers has an acid group, such as those which areobtainable under the trademarks AMPHOMER® and AMPHOMER® LV-71 ofNational Starch, U.S.A.

[0027] Further examples of suitable copolymers include copolymers ofacrylic acid, methacrylate and methacrylamideopropyltrimethylammoniumchloride (INCI: polyquaternium-47), copolymers made fromacrylamidopropyltrimethyl ammonium chloride and acrylates or copolymersmade from acrylamide, acrylamidopropyltrimethylammonium chloride,2-amidopropylacrylamide sulfonate and dimethylaminopropylamine (INCI:Polyquaternium-43). Suitable polymers made with monomers carryingbetaine groups, such as copolymers of methacryloylethylbetaine and twoor more monomers made from acrylic acid or their simple esters, knownunder the INCI designation methacryloyl ethyl betaine/acrylatescopolymer.

[0028] The composition according to the invention is preferably providedin an aqueous, alcoholic or an aqueous-alcoholic medium with preferablyat least 10 percent by weight water and preferably up to a maximumamount of 40 percent by weight alcohol. Lower univalent or multivalentalcohols suitable for cosmetic purposes and having from one to fourcarbon atoms, such as ethanol and isopropanol, may be used as thealcohol. The composition according to the invention has a pH of greaterthan 7, preferably at least 7.3. At lower pH values the neutralizationof the acid groups of the itaconic acid monoester copolymers (A) isinsufficient and the consistency is too thin. Values of pH between 7.5and 8.5 are particularly preferred. In a preferred embodiment the gelcontains multivalent alcohols for further improvements in luster,preferably those with 2 to 5 carbon atoms and with 2 to 5 hydroxy groupsin an amount of 0.1 to 15 percent by weight, preferably from 1 to 10percent by weight. Glycerol, ethylene glycol and propylene glycol,especially 1,2-propylene glycol, are especially preferred.

Rheological Properties

[0029] The composition of the invention is characterized by aparticularly advantageous, special rheological behavior, whereby boththe application properties and the haptic properties are improved. Aportion of the gel may be dispensed “dry” from its container by pullingoff or tearing off, without dripping or becoming stringy. Unintended runoff from a containing tube or on inclined surfaces, such as the hand andhair is minimized. Physically the gel according to the invention ischaracterized by the occurrence of a maximum in the viscosity curve withincreasing shear rate. The maximum is typically at shear rates in thevicinity of 0.1 to 5.0, preferably from 0.15 to 2.0, s⁻¹, at atemperature of 25° C. During shear stress the flow curve has a turningpoint where the viscosity attains a maximum value. Another specialcharacteristic is that the viscosity curve for increasing shear rateintersects the curve for decreasing shear rate. The crossing pointtypically is approximately at a shear rate in the vicinity of 0.05 to 3,preferably 0.1 to 2, s⁻¹. At high shear rate the forward curve liesabove the back curve and the gel is thixotropic. At low shear rate theforward curve lies under the back curve and the gel is anti-thixotropic.The viscosity and flow curves can be measured, for example with a BohlinCS System Rheometer, in which the shear rate increases with a linearspeed of from 0 to a maximum value, e.g., of about 100 s⁻¹, andsubsequently is lowered again to the null point, under isothermalconditions (25° C.).

[0030] The sole FIGURE shows a typical example of a measurement diagramtaken with a Bohlin CS System Rheometer at temperature of 25° C. for agel according to example 2. The viscosity (viscosity on left axis,measured values shown as square symbols) and shear stress (shear stresson right axis, measured values shown with rhombus symbols) are plottedversus shear rate (X-axis). The arrows next to the curves show thedirection of the change of the shear rate. With a shear rate of about0.6 s⁻¹ the viscosity curve has a maximum and the flow curve (shearstress) has a turning point. The forward and the back curves have anintersection at about 0.7 s⁻¹.

[0031] The viscosity of the gel preferably amounts to from 1000 to100,000 mPa.s, especially preferably from 2000 to 50,000 mPa.s, and mostpreferably from 2,500 to 15,000 mPa.s, measured as dynamic viscositywith a Haake VT-550 Rheometer, measurement body SV-DIN at a temperatureof 25° C. and a shear rate of 50 s⁻¹.

[0032] The compositions according to the invention can also containconventional additive ingredients suitable for hair treatmentcompositions. These additive ingredients include, e.g. wetting agents oremulsifiers, from the classes of nonionic, anionic, cationic oramphoteric surfactants, such as fatty alcohol sulfates, alkyl benzenesulfonates, alkyltrimethylammonium salts, alkyl betaines, in an amountof from 0.1 to 15 percent by weight; moisturizers; perfume oils in anamount of 0.1 to 1.0 percent by weight; turbidity-imparting agents, suchas ethylene glycol distearate, in an amount of about 0.2 to 5.0 percentby weight; pearlescence-imparting agents, such as a mixture of fattyacid monoalkylolamide and ethylene glycol distearate, in an amount offrom about 1.0 to 10 percent by weight; bactericidal and fungicidalagents, for example, 2,4,4 trichloro-2-hydroxydiphenyl ether or methylchloroisothiazolone, in an amount of from 0.01 to 1.0 percent by weight;thickeners, such as coconut fatty acid diethanol amides, in an amount ofabout 0.2 to 3.0 percent by weight; buffer substances, such as sodiumcitrate or sodium phosphate, in an amount of from 0.1 to 1.0 percent byweight; colorants, for example, fluorescein sodium salt, in an amount ofabout 0.1 to 1.0 percent by weight; care materials, such as plant andvegetable extracts, protein and silk hydrolyzates, lanolin derivativecompounds, in an amount of 0.1 to 5 percent by weight; physiologicallycompatible silicone derivative compounds, such as volatile ornon-volatile silicone oils or high-molecular-weight siloxane polymers,in an amount of from 0.05 to 20 percent by weight; light protectivematerials, antioxidants, radical trapping agents, anti-flaking activeingredients, in an amount of about 0.01 to 4 percent by weight; fattyalcohols; luster-imparting agents; vitamins; softening agents;combability-improving agents, de-fatting agents and anti-foaming agents.

[0033] The composition according to the invention is preferably in theform of a clear, transparent or at least translucent gel. The gel can becolored or colorless.

[0034] The composition according to the invention is characterized byrheological properties, which particularly manifest themselves in anattractive appearance and pleasant haptic properties. The compositionmay be easily packaged in a tube, a pan or a can and can be dispensedfrom these containers without leaving a residue, in contrast tocurrently known commercially available gels packaged in tubes. A portionof the gel according to the invention may pulled off, broken off orseparated, without dripping or after-running. The composition is easilydistributed on the hair. When formulated as a hair treatment agent itdoes not load the hair and is especially good for fine hair. It providesa sufficient hold for the hairstyle, without adhering to the hair orloading it. Fine hair becomes full and voluminous. As a hair fixing gelthe hair treatment composition provides improved fixing properties andespecially a clearly better luster than commercial gels formulated on acarbomer basis.

[0035] In a special embodiment the gel according to the invention issuitable for simultaneously fixing and temporarily coloring hair. Itcontains additionally at least one temporary hair dye pigment. A“temporary hair coloring” means a color change of human hair, whichlasts until the next hair washing and which can be removed again bywashing the with conventional shampoos. The pigments are, preferably,contained in the composition in an amount of from 0.01 to 25 percent byweight, especially preferably in an amount of 5 to 15 percent by weight.The pigments are preferably micro-pigments, not nano-pigments. Thepreferred particle size amounts to from 1 to 200 μm, especially from 3to 150 μm, especially preferably from 10 to 100 μm.

[0036] The pigments are practically insoluble coloring agents and can beinorganic or organic. Also inorganic-organic mixed pigments may be used.Inorganic pigments are preferable. The advantage of the inorganicpigments is their outstanding light-resistance, weather-resistance andtemperature-resistance. The inorganic pigments can be of natural origin,for example chalk, ocher, umber, green earth, burnt siena or graphite.The pigments can be white pigments, such as titanium dioxide or zincoxide; black pigments, such as iron oxide black; fancy or multi-coloredpigments, such as ultramarine or iron oxide red; lustrous pigments,metal effect pigments, pearlescent pigments as well as fluorescene orphosphorescent pigments. Preferably at least one pigment is a colored,non-white pigment. Metal oxides, metal hydroxides and metal oxidehydrates, mixed phase pigments, sulfur-containing silicates, metalsulfides, complex metallo-cyanides, metal sulfates, metal chromates andmetal molybdates and metals themselves (bronze pigments) are suitable.In particular, titanium dioxide (C.I. 77891), black iron oxide (C.I.77499), yellow iron oxide (C.I. 77492), red and brown iron oxide (C.I.77491), manganese violet (C.I. 77742), ultramarine (sodium aluminumsulfosilicate, C.I. 77007, Pigment Blue 29), chromium oxide hydrate(C.I. 77289), Iron Blue (Ferric ferrocyanide, C.I. 77510) and carmine(cochineal), are all suitable pigments.

[0037] Pigments based on mica and/or isinglass, which are coated with ametal oxide or metal oxychloride, such as titanium dioxide or bismuthoxychloride and if necessary other color-imparting materials, such asiron oxides, iron blue, ultramarine, carmine, etc, whose colors can bemodified by changing the thickness of the coating, are especiallypreferred. Pigments of this sort are marketed, for example, under thetrademark, Rona®, Colorona®, Dichrona® and Timiron® by the firm, Merck,Germany.

[0038] Organic pigments are, for example, the natural pigments, Sepia,gamboge, charcoal, Kasseler brown, indigo, chlorophyl and other plantpigments. Synthetic organic pigments include, for example, azo pigments,anthrquinoid pigments, indigoid pigments, dioxazine, quinacridone,phthalocyanine isoindolinone pigments, perylene pigments, perinonepigments, metal complex pigments, alkali blue pigments anddiketopyrrolopyrrole pigments.

BRIEF DESCRIPTION OF THE DRAWING

[0039] The objects, features and advantages of the invention areexplained in this description with the aid of the following sole FIGURE,which is graphical illustration showing the rheological behavior of ahair treatment gel according to the invention, particularly thedependence of viscosity and shear stress on shear rate.

EXAMPLES

[0040] The following examples should clearly illustrate the subjectmatter of the invention. The polymer content given in the examples isbased on the solid content. Example 1: Hair Gel A B PVA/VA Copolymer 8.0g 8.0 g Acrylates/Ceteth-20 3.0 g — Itaconate copolymer Carbomer — 0.5 gPropylene glycol 2.7 g 2.7 g Aminomethylpropanol 1.425 g 0.5 g Water to100 g To 100 g

[0041] Two hair gels of comparable viscosity were prepared and comparedin regard to their hair luster and hair fixing power. Gel A is accordingto the invention and gel B is a commercial gel on the basis of carbomer.For luster measurement 0.5 g portions of gel were applied to respective2 g hair strand samples. The strand samples were dried over night at 65percent relative humidity and at 20° C. The luster measurement tookplace by directing a parallel light beam to a test surface and measuringthe angular distribution of the reflected light and of the lightscattered in or under the surface. The higher the amount of directlyreflected light and the less the amount of scattered light, the higherthe luster. A luster classification can occur by measurement andevaluation of the angular distribution of the light returned from thetest surface. A small angular distribution (smaller half-width, HWB)means a greater luster and a broad angular distribution (largerhalf-width, HWB) means a poorer luster. The measurement of the angulardistribution occurs with a digital camera, the data are read into acomputer and evaluated with image processing software (Optimate 5.2).Six measurements were performed per sample and the average values wereformed. Untreated Strands: HWB = 40° Sample A: HWB = 35° Sample B: HWB =37°

[0042] The change of thickeners leads surprisingly to an increase ofhair luster. The measurement results correlate with a visual lusterevaluation of the strands by a panel of experts experienced in theevaluation of hair quality.

[0043] The comparison of the fixing performance occurs by measurement ofthe curl retention CR. The gel portions were applied to the respectivehair strand samples. The strands were wound on spiral curlers after anacting time of 10 minutes, and stored for 30 minutes at 70° C. and forone hour at 20° C. and a relative humidity of 85%. Subsequently thestrands were removed from the curlers and loaded with a 50 mg weight andsuspended. The lengths of the strand samples were measured after 5 hoursand the curl retentions were calculated from the measured lengths by thefollowing formula.

CR=(L₀−L_(t))/(L₀−L₁)*100%

[0044] wherein L₀=Length of the stretched strand samples;

[0045] L_(t)=Length of the suspended strand samples; and

[0046] L₁=Length of the wound strand samples.

[0047] Three measurement values were obtained per sample and the resultswere averaged. Untreated strand samples: CR (5h) = 42%; CR (24h) = 21%;Sample A: CR (5h) = 75%; CR (24h) = 60%; Sample B: CR (5h) = 47%; CR(24h) = 29%.

[0048] The change or replacement of the thickener leads to surprisinglyhigher curl retention in the hair sample treated with gel sample Aaccording to the invention. Example 2: Hair Gel PVA/VA Copolymer 1.0 gAcrylates/Ceteth-20 3.0 g Itaconate copolymer Aminomethylpropanol 1.6 gWater To 100 g Viscosity about 6550 mPa · s (25° C.)

[0049] The flow and viscosity curves with increasing and decreasingshear rates in the vicinity of 0 to 20 s⁻¹ are shown in FIG. 1. Example3: Hair Gel PVA/VA Copolymer 2.0 g Acrylates/Ceteth-20 1.5 g Itaconatecopolymer Aminomethylpropanol 0.8 g PEG-40 Hydrogenated 0.3 g Castor OilPerfume 0.2 g Water To 100 g Viscosity about 2600 mPa · s (25° C.)

[0050] Example 4: Hair Gel VA/Crotonates 1.0 g Copolymer(Luviset ® 66)Acrylates/Ceteth-20  2.25 g Itaconate copolymer Aminomethylpropanol 1.4g PEG-40 Hydrogenated 0.3 g Castor Oil Perfume 0.2 g Water To 100 gViscosity about 5800 mPa · s (25° C.)

[0051] Example 5: Hair Gel VA/Crotonates 1.0 g Copolymer(Luviset ® 66)Acrylates/Ceteth-20  2.25 g Itaconate copolymer Aminomethylpropanol 1.4g Polysorbate 40 0.8 g Timiron ® Gold Plus MP-25 0.2 g Water To 100 gViscosity about 5600 mPa · s (25° C.)

[0052] Example 6: Hair Gel Octylacrylamide/acrylates/ 2.5 gButylaminoethyl methacrylate copolymer (Amphomer ®) Acrylates/Ceteth-201.5 g Itaconate copolymer Aminomethylpropanol  1.23 g FD&C Green No. 3(C.I. 42053) 0.1 g Water To 100 g Viscosity about 3600 mPa · s (25° C.)

[0053] Example 7: Hair Gel Polyvinylpyrrolidone K80 2.0 gAcrylates/Ceteth-20  3.75 g Itaconate copolymer Aminomethylpropanol 2.0g Polysorbate 40 0.8 g Perfume 0.1 g Water To 100 g Viscosity about14200 mPa · s (25° C.)

[0054] The disclosure in German Patent Application 101 42 476.0 of Aug.31, 2001 is incorporated here by reference. This German PatentApplication describes the invention described hereinabove and claimed inthe claims appended hereinbelow and provides the basis for a claim ofpriority for the instant invention under 35 U.S.C. 119.

[0055] While the invention has been illustrated and described asembodied in a hair treatment gel containing itaconic acidmonoester/acrylate copolymer, it is not intended to be limited to thedetails shown, since various modifications and changes may be madewithout departing in any way from the spirit of the present invention.

[0056] Without further analysis, the foregoing will so fully reveal thegist of the present invention that others can, by applying currentknowledge, readily adapt it for various applications without omittingfeatures that, from the standpoint of prior art, fairly constituteessential characteristics of the generic or specific aspects of thisinvention.

[0057] What is claimed is new and is set forth in the following appendedclaims.

We claim:
 1. An aqueous hair treatment gel having a viscosity of atleast 1000 mPa.s, as measured at 25° C. and at a shear rate of 50 s⁻¹, apH of greater than 7 and which contains water and at least 0.5 percentby weight of at least one copolymer of a first monomer and a secondmonomer, said first monomer being an itaconic acid monoester of formulaCH₂═C(COOR¹)CH₂COOR², wherein one of R¹ and R² represents hydrogen andanother of R¹ and R² represents —(CH₂CH₂O)_(x)—R³, x is a number between1 to 100 and R³ is an alkyl group having 8 to 30 carbon atoms, and saidsecond monomer being an acrylate monomer; and at least one non-ionic,anionic, zwitterionic or amphoteric hair-fixing polymer; but which doesnot contain a combination of an acrylate/Ceteth-20-itaconate copolymer,cellulose acetate phthalate andHO—(CH₂CH₂O)₇₅—(CH(CH₃)CH₂O)₃₀—(CH₂CH₂O)₇₅—H.
 2. The aqueous hairtreatment composition as defined in claim 1, containing from 1.5 to 10percent by weight of said at least one copolymer of said first monomerand said second monomer.
 3. The aqueous hair treatment composition asdefined in claim 1, containing from 0.1 to 15 percent by weight of saidat least one non-ionic, anionic, zwitterionic or amphoteric hair-fixingpolymer.
 4. The aqueous hair treatment composition as defined in claim1, and having a rheological behavior at 25° C. such that said viscosityfirst increases with said shear rate from zero when said shear rateincreases from zero, then passes through a maximum value and, afterpassing through the maximum value, said viscosity decreases as saidshear rate increases further.
 5. The aqueous hair treatment compositionas defined in claim 4, wherein said maximum value occurs when said shearrate is between 0.1 and 5 s⁻¹ with increasing shear rate.
 6. The aqueoushair treatment composition as defined in claim 1, wherein said R³represents an alkyl group having 12 to 20 carbon atoms and said xrepresents a number from 10 to
 40. 7. The aqueous hair treatmentcomposition as defined in claim 1, wherein said second monomer isselected from the group consisting of acrylic acid, methacrylic acid,acrylic acid alkyl esters and methacrylic acid alkyl esters, and whereinsaid alkyl esters contain alkyl groups having from 1 to 10 carbon atoms.8. The aqueous hair treatment composition as defined in claim 1, whereinsaid at least one non-ionic, anionic, zwitterionic or amphoterichair-fixing polymer is polyvinylpyrrolidone, vinylpyrrolidone/vinylacetate copolymer, vinyl acetate/crotonic acid copolymer, a terpolymerof vinyl acetate, crotonate and vinyl alkanoate, a partially esterifiedcopolymer of vinylmethyl ether and maleic acid anhydride, a copolymer ofacrylic or methacrylic acid with an alkylacrylate or anN-alkylacrylamide and a polystyrene sulfonate or a copolymer of analkylacrylamide, alkylaminoalkyl methacrylate and two or more monomericcompounds; wherein said monomeric compounds are each selected from thegroup consisting of acrylic acid, methacrylic acid, alkyl esters ofacrylic acid and alkyl esters of methacrylic acid; and wherein at leastone of said monomeric compounds contains an organic acid group and saidalkyl esters contain from one to four carbon atoms.
 9. The aqueous hairtreatment composition as defined in claim 1, substantially free ofcationic polymers.
 10. The aqueous hair treatment composition as definedin claim 1, further comprising at least one alcoholic ingredientselected from the group consisting of monovalent alcohols with from 1 to4 carbon atoms and polyvalent alcohols with from 2 to 5 carbon atoms.11. An aqueous hair treatment gel having a viscosity of at least 1000mPa.s, as measured at 25° C. and at a shear rate of 50 s⁻¹, a pH ofgreater than 7 and which contains water and from 0.5 to 20 percent byweight of at least one copolymer of a first monomer and a secondmonomer, said first monomer being an itaconic acid monoester of formulaCH₂═C(COOR¹)CH₂COOR², wherein one of R¹ and R² represents hydrogen andanother of R¹ and R² represents —(CH₂CH₂O)_(x)—R³, x is a number between1 to 100 and R³ is an alkyl group having 8 to 30 carbon atoms, saidsecond monomer being selected from the group consisting of acrylic acid,methacrylic acid, alkyl esters of acrylic acid and alkyl esters ofmethacrylic acid, said alkyl esters containing alkyl groups having fromone to ten carbon atoms; and wherein said viscosity first increases assaid shear rate increases from zero, then said viscosity passes througha maximum value and, after passing through the maximum value, saidviscosity decreases as said shear rate increases further; but which doesnot contain a combination of an acrylate/Ceteth-20-itaconate copolymer,cellulose acetate phthalate andHO—(CH₂CH₂O)₇₅—(CH(CH₃)CH₂O)₃₀—(CH₂CH₂O)₇₅—H.
 12. An aqueous hairtreatment gel having a viscosity of at least 1000 mPa.s, as measured at25° C. and at a shear rate of 50 s⁻¹, a pH of greater than 7 and whichcontains water and at least 0.5 percent by weight of at least onecopolymer of a first monomer and a second monomer, said first monomerbeing an itaconic acid monoester of formula CH₂═C(COOR¹)CH₂COOR²,wherein one of R¹ and R² represents hydrogen and another of R¹ and R²represents —(CH₂CH₂O)_(x)—R³, x is a number between 1 to 100 and R³ isan alkyl group having 8 to 30 carbon atoms, and said second monomerbeing an acrylate monomer; and at least one hair-coloring pigment. 13.The aqueous hair treatment composition as defined in claim 12,containing from 0.01 to 25 percent by weight of said at least onehair-coloring pigment and wherein said at least one hair-coloringpigment is a metal oxide pigment, ultramarin, a lustrous pigment, ametal effect pigment, a pearlescent pigment, a fluorescene pigment, aphosphorescent pigment, a metal hydroxide pigment, a metal oxide hydratepigment, a mixed phase pigment, a sulfur-containing silicate pigment, ametal sulfide pigment, a metal cyanide complex pigment, a metal sulfatepigment, a metal chromate pigment, a metal molybdate pigment, a bronzepigment, carmine or a mica-based pigment, and wherein said mica-basedpigment is coated with a metal oxide layer or metal oxychloride layerand, optionally, with iron oxide, iron blue, said ultramarine or saidcarmine, and said layer has a layer thickness according to apredetermined color effect.
 14. An aqueous hair treatment gel having aviscosity of at least 1000 mPa.s, as measured at 25° C. and at a shearrate of 50 s⁻¹, a pH of greater than 7 and which contains water and atleast 0.5 percent by weight of at least one copolymer of a first monomerand a second monomer, said first monomer being an itaconic acidmonoester of formula CH₂═C(COOR¹)CH₂COOR², wherein one of R¹ and R²represents hydrogen and another of R¹ and R² represents—(CH₂CH₂O)_(x)—R³, x is a number between 1 to 100 and R³ is an alkylgroup having 8 to 30 carbon atoms, and said second monomer being anacrylate monomer; and at least one non-ionic, anionic, zwitterionic oramphoteric hair-fixing polymer.
 15. An aqueous hair treatment gel havinga viscosity of at least 1000 mPa.s, as measured at 25° C. and at a shearrate of 50 s⁻¹, a pH of greater than 7 and which contains water and from0.5 to 20 percent by weight of at least one copolymer of a first monomerand a second monomer, said first monomer being an itaconic acidmonoester of formula CH₂═C(COOR¹)CH₂COOR², wherein one of R¹ and R²represents hydrogen and another of R¹ and R² represents—(CH₂CH₂O)_(x)—R³, x is a number between 1 to 100 and R³ is an alkylgroup having 8 to 30 carbon atoms, and said second monomer beingselected from the group consisting of acrylic acid, methacrylic acid,alkyl esters of acrylic acid and alkyl esters of methacrylic acid, saidalkyl esters containing alkyl groups having from one to ten carbonatoms; and wherein said viscosity first increases with said shear ratefrom zero when said shear rate increases from zero, then passes througha maximum value and, after passing through the maximum value, saidviscosity decreases as said shear rate increases further.